Element-specific behaviour and sediment properties modulate transfer and bioaccumulation of trace elements in a highly-contaminated area (Augusta Bay, Central Mediterranean Sea).

High sediment contamination in the coastal area of Priolo Bay, adjacent to the highly-polluted Augusta Harbour, poses serious risks for the benthic communities inhabiting the area. Nevertheless, the transfer of trace elements and consequent bioaccumulation in the biota is an overlooked issue. This study aimed to assess the transfer and bioaccumulation patterns of As, Cd, Ni and Hg to the dominant macroalgae and benthic invertebrates of Priolo Bay. Results revealed different patterns among trace elements (TEs), not driven by sediment contamination but rather by element-specific behaviour coupled with sediment physicochemical properties. Specifically, As accumulated in macroalgae but not in invertebrates, indicating bioavailability of dissolved As only, and a lack of effective trophic transfer. Ni was confined to surface sediment and transfer to biota was not highlighted. Cd and Hg showed the highest concentrations in invertebrates and bioaccumulated especially in filter feeders and carnivores, revealing the importance of suspended particulate and diet as transfer pathways. Total organic carbon (TOC), fine-grained sediments and redox potential were the most important sediment features in shaping the sediment contamination spatial patterns as well as those of TE transfer and bioaccumulation. In particular, As and Cd transfer to macroalgae, and especially Hg bioaccumulation in benthic invertebrates was controlled by sediment properties, resulting in limited transfer and accumulation in the most contaminated stations.

Effect of solid waste landfill organic pollutants on groundwater in three areas of Sicily (Italy) characterized by different vulnerability.

The aim of this study was to obtain information on the presence and levels of hazardous organic pollutants in groundwater located close to solid waste landfills. Eighty-two environmental contaminants, including 16 polycyclic aromatic hydrocarbons (PAHs), 20 volatile organic compounds (VOCs), 29 polychlorinated biphenyls (PCBs), 7 dioxins (polychlorinated dibenzo-p-dioxins, PCDDs) and 10 furans (polychlorinated dibenzofurans, PCDFs) were monitored in areas characterised by different geological environments surrounding three municipal solid waste landfills (Palermo, Siculiana and Ragusa) in Sicily (Italy) in three sampling campaigns. The total concentrations of the 16 PAHs were always below the legal threshold. Overall, the Fl/Fl + Py diagnostic ratio revealed that PAHs had a petrogenic origin. VOC levels, except for two notable exceptions near Palermo landfill, were always below the legal limit. As concerns PCB levels, several samples were found positive with levels exceeding the legal limits. It is worth noting that the % PCB distribution differs from that of commercial compositions. In parallel, some samples of groundwater containing PCDDs and PCDFs exceeding the legal threshold were also found. Among the 17 congeners monitored, the most abundant were the highest molecular weight ones.

Trace element storage capacity of sediments in dead Posidonia oceanica mat from a chronically contaminated marine ecosystem.

Posidonia oceanica mat is considered a long-term bioindicator of contamination. Storage and sequestration of trace elements and organic carbon (Corg ) were assessed in dead P. oceanica mat and bare sediments from a highly polluted coastal marine area (Augusta Bay, central Mediterranean). Sediment elemental composition and sources of organic matter have been altered since the 1950s. Dead P. oceanica mat displayed a greater ability to bury and store trace elements and Corg than nearby bare sediments, acting as a long-term contaminant sink over the past 120 yr. Trace elements, probably associated with the mineral fraction, were stabilized and trapped despite die-off of the overlying P. oceanica meadow. Mat deposits registered historic contamination phases well, confirming their role as natural archives for recording trace element trends in marine coastal environments. This sediment typology is enriched with seagrass-derived refractory organic matter, which acts mainly as a diluent of trace elements. Bare sediments showed evidence of inwash of contaminated sediments via reworking; more rapid and irregular sediment accumulation; and, because of the high proportions of labile organic matter, a greater capacity to store trace elements. Through different processes, both sediment typologies represent a repository for chemicals and may pose a risk to the marine ecosystem as a secondary source of contaminants in the case of sediment dredging or erosion. Environ Toxicol Chem 2017;36:49-58. © 2016 SETAC.

Premature aging in bone of fish from a highly polluted marine area.

Fish species have attracted considerable interest in studies assessing biological responses to environmental contaminants. In this study, the attention has been focussed on fishbone of selected fish species from a highly polluted marine area, Augusta Bay (Italy, Central Mediterranean) to evaluate if toxicant elements had an effect on the mineralogical structure of bones, although macroscopic deformations were not evident. In particular, an attempt was made to evaluate if bone mineral features, such as crystallinity, mineral maturity and carbonate/phosphate mineral content, determined by XR-Diffraction and FT-IR Spectroscopy, suffered negative effects due to trace element levels in fishbone, detected by ICP-OES. Results confirmed the reliability of the use of diffractometric and spectroscopic techniques to assess the degree of crystallinity and the mineral maturity in fishbone. In addition, in highly polluted areas, Hg and Cr contamination induced a process of premature aging of fishbone, altering its biochemical and mineral contents.

The key role played by the Augusta basin (southern Italy) in the mercury contamination of the Mediterranean Sea.

The Augusta basin, located in SE Sicily (southern Italy), is a semi-enclosed marine area, labelled as a highly contaminated site. The release of mercury into the harbour seawater and its dispersion to the blue water, make the Augusta basin a potential source of anthropogenic pollution for the Mediterranean Sea. A mass balance was implemented to calculate the HgT budget in the Augusta basin. Results suggest that an average of ∼0.073 kmol of HgT is released, by diffusion, on a yearly basis, from sediments to the seawater, with a consequent output of 0.162 kmol y(-1) to coastal and offshore waters; this makes the Augusta area an important contributor of mercury to the Mediterranean Sea. Owing to the geographical location of the Augusta basin, its outflowing shelf-waters are immediately intercepted by the surface Atlantic Ionian Stream (AIS) and mixed with the main gyres of the eastern Mediterranean Sea, thus representing a risk for the large-scale marine system.

Distribution of REEs in box-core sediments offshore an industrial area in SE Sicily, Ionian Sea: evidence of anomalous sedimentary inputs.

The distribution of rare earth elements and yttrium (REEs+Y) has been investigated in box-core sediments recovered from four stations in the Sicilian coastal zone seawards of Augusta, one of the most industrialized and contaminated areas in the Mediterranean region. Shale-like REE patterns and low Y/Ho ratios (close to the chondritic ratio) suggest a dominant terrigenous (geogenic) source for REE. Slight enrichment of LREE over the HREE is interpreted as due to preferential adsorptive transfer of LREE from seawater to sediment particles. Samples from offshore cores exhibit slightly positive Gd and negative Ce anomalies. It is here hypothesized that main drivers of anthropogenic Gd flux towards the offshore are dredged contaminated materials that, recovered from the Augusta Bay, have been repeatedly discharged offshore. Consistent with the redox-chemistry of Ce, these anomalous sedimentary inputs induce a decrease of O(2) concentration in the sediment, which in turn triggers Ce regeneration.

Possible impacts of Hg and PAH contamination on benthic foraminiferal assemblages: an example from the Sicilian coast, central Mediterranean.

The Palermo and Augusta urban/industrial areas (Sicily) are examples of contaminated coastal environments with a relatively high influx of unregulated industrial and domestic effluents. Three sediment box-cores were collected offshore of these urban/industrial areas in water depths of 60-150 m during two cruises (summers 2003/2004), dated by (210)Pb and (137)Cs, and analysed for total mercury concentration and total polycyclic aromatic hydrocarbon (PAH) concentration. Benthic foraminiferal assemblages were also examined (in terms of their distribution and morphology) to assess the potential use of benthic foraminifera as bioindicators of pollutant input and environmental change in these Mediterranean shelf environments. The Hg and PAHs vs depth profiles show a clear increase in concentration with decreasing depth. Most of the sediments are highly enriched in mercury and show concentrations more than 20 times the background mercury value estimated for sediments from the Sicily Strait. The Hg and PAH concentrations appear to be potentially hazardous, grossly exceeding national and international regulatory guidelines. A reduction in abundance of benthic foraminifera, increasing percentages of tests with various morphological deformities, and the dominance of opportunistic species in more recent sediments can be correlated to anthropogenic impact.

Mercury levels in sediments of central Mediterranean Sea: a 150+ year record from box-cores recovered in the Strait of Sicily.

To evaluate the degree of anthropogenic mercury pollution, Hg contents have been measured for box-core sediments sampled along three nearshore-offshore transects in the Strait of Sicily and well constrained for their mineralogy, bulk geochemistry and TOC%. Hg values are generally low (from 15 to 70 microg kg(-1)); however, depth profiles clearly display upcore rising concentrations (up to 202 microg kg(-1) near the SE Sicily coast) that are attributed to anthropogenic load. Based on (210)Pb chronology, these trends are more dramatic across the last 20-30 years. Geogenic influence is thought to explain some anomalies related to volcanic emission and geothermal activity. Combined effects due to eastward flowing of the Modified Atlantic Water (MAW) and sea bottom morphology drove major anthropogenic accumulation.